Metal compounds of azo dyestutfs



dyestuffs containing metal thus obtained are dis-- Patented Nov. 12,1940 2 221 350 UNITED STATES PATENT OFFICE,

METAL COMPOUNDS OFAZO DYESTUFFS Max Schmid, Riehen, near Basel, Switzerland, as-

signor to the firm Society of Chemical Industry in Basle, Basel, Switzerland No Drawing. Application September 27, 1937, Se-

rial No. 166,021. In Switzerland October 3, 1936 17 Claims. (01. 260-147) According to this invention valuable products 5-nitro-6-- chlorbenzene, 1 L hydroxy -;2 aminoare obtainedby treating with an agent yielding 4 methyl benzene, 1 hydroxy 2 amino 4- metal, suchasa compound of copper, chromium, nitro-6-chlorobenzene, l-hydroxy-2eamino-4-ninickel, iron or cobalt, in substance or on the fibre, trobenzene-G-sulfonic acid, 1-hydroxy-2-aminoan azo-dyestufi which is obtainable by the action fi-nitrobenzene- 4 -sulfonic acid, 1 hydroxy 2 of such a diazo-compound of the benzene and aminobenzene-l-sulfamide, 1-hydroxy-2-amino-, naphthalene series which contains in ortho-posinaphthalene-4:8-disu1fonic acid, ,Z-hydroxy -1 tion to the diaZo-group a substituent which is aminonaphthalene-4-sulfonic acid, 2-hydroxy-1- capable of forming stable lakes with the azoamino-finitronaphthalene 4 -sulfonic acid, 1-

group formedjmuch as an ortho-hydroxy or oraminobenzene ,-2- carboxylic acid, 1 amino -.4 tho-carboxy-diazo compound on a 1-aryl-5-pyrachlorbenzene-Z-carboxylic acid, l-aminol-nitrozolone which itself is obtainable by condensation benzene-Z-carboxylic acid, l-amino 7 4 benzoyL of a fi-carbonyl-carboxylic acid ester with a hyamino-2-carboxy1ic acid, 4-amino-3-carboxy1icdrazine of the general formula azo-benzene-P-sulfonic acid, aminosulfobenzoic acid (NH2:1, 0OOH:2,SOsH:4), 2-aminonaph- NHPNEF thalene-B-carboxylic acid,-and so on.

I Among the ,o-carbonylecarboxylic acid esters available for preparing the 1-ary1-5-pyrazolones which canbe usedfor the synthesis of the par ent dyestuffs there may be named formyl acetic acid esterafurthermore p-keto-carboxylic acid esters, such .as ethyl-aceto-acetate, ethyloxal acetate, ethylbenzoylacetate, terephthaloyldis acetic acid ethyl ester, and so on. Among the hydrazines which likewise are used for preparing the 1-aryl-5-pyrazolones used for the synthesis y i g nd y their excellent amnity for Vege of the parent dyestuffs there may be namedsuch roducts s: table fibres, such as cotton, flax, ramie, and for p fibres of regenerated cellulose, such as artificial NHPNH OHPOH silks, for example viscose artificial silk or cupramg monium artificial silk.

Among the ortho-hydroxy and ortho-carboxydiazo compounds which come into consideration NHPNEF for the preparation of the azo-dyestufis forming I ,1 the parent materials of the invention there may i be named quite generally those derived from orthq-aminophenols or orthO-aminonaphthols or NHPNH- 3:

from ortho aminocarboxylicacids of the benzene I or naphthalene series, for, example 1-hydr0xy-2- 033 SOaH in which'y represents a -CH=CH group or a CH2CH.2 group and 2 represents a group which is formed by reduction of a nitro-group in combination with a condensation, such as an azoor azoxy-group or an amino-group substituted by the residue of an organic acid. The new azotinguished by the high fastness to light of their aminobenzene, 1-hydroxy-2-amino- 4 chlorbenzene, 1-hydroxy-2-amino-4 -nitrobenzene, 1 hy- NHPNH droxy-Z-amino -5- nitrobenzene, 1 -hydroxy -,2 amino-4zfi-dinitrobenzene, l-hydroxy -2 amino Quite generally, however, it is more advantageous first to combine the nitrohydrazine or the aminohydrazine with one of the aforesaid ,B-carbonyl-carboxylic acid esters and then to conduct the reduction of the nitro-group in combination with a condensation reaction. This may occur, for example, by cautious reduction by means of grape sugar, the course of the reactionrbeing presumed to consist in the reduction of a part of the product to the amino-group, which then condenses with the unreduced or only partially reduced portions to produce an am or azoxy 7 compound (compare Formulae 21 and 22 below) (The protection of such dyestuffs is the object of my divisional application Serial No. 263,796 filed March 23, 1939), or the operation may consist in complete reduction of the nitro-group to the NI-Iz-group and subsequent condensation, for example with a halogen compound which converts the. NHz-group into a NH--( 3'-b-group in a which a. stands for metalloid whose atomic weight is not less than 14 and not greater than 16, and b stands for an organic residue of the aliphatic, aromatic, cycloaliphatic, heterooyclic, araliphatic series and so on. Such products constitute acyl derivatives or the amidines which chemically are closely relatedther'eto. As is known, the introduction of such residues into intermediate products or dyestuffs increase the affinity for vegetable fibre. Such residues can be introduced by acylation, for example by treatment with benzoyl. chloride, phenylacetyl chloride, cinnamyl chloride, succinyl chloride, butyryl chloride, hexahydrobenzoyl chloride, furane-carboxylic acid chloride, benzimino ether, by treatment with phosgene' or thio'phosg'ene or by treatment with heterocyclic products of the nature of amidine halides, such as 'cyanuric acid chloride, cyanuric acid bromide, tribromopyrimidine, 2:6-dichloroe-meth'ylpyridine, dichloroquinazoline, and so on.

Such dyestuffs containing heterocyclic rings are also the object of my divisional application Serial No. 263,795 filed March 23, 1939.

Particularly valuable products result when the condensation is conducted in such a manner that the residue b is so constituted that itco'ntains an azochromophore or is adapted to couplewith 6 diazo compounds to produce azo-dyestuffs.

There are thus obtained l-aryl-5-pyrazolones in which the aryl residue has the general formula:

SOaH S 03H CHz-group and 2 stands for a nitro-group in 60 combination with a condensation. Such pyrazolone derivatives are, for example:

SOsH

3 O OH:

S OaH SOzH (s) cm 80:41.1 SOaH SOzH From a comparison of the pyrazolone nuclei of the products of the Formulae 1-7 with those of the products resulting from the reduction of a nitro-group together with a condensation shown in Formulae 523, all of which are given by way of example, it is evident how numerous are the intermediate products for making the dyestufis forming the'parent materials for the invention; 1

regard must further be had to the fact that the aryl residue of the pyrazolones may belong either to the stilbene or to the dibenzyl series. It is also possible first to convert the I-aryl-S-pyrazolones from the aforesaid nitroor amino-hydrazines by coupling with one of the diazo compounds already referred to into azo-dyestuffs the general formula:

S 0311 S 0311 H in which R. stands for an aromatic nucleus of the benzene or naphthalene series, :0. stands for an OH- or a COOI-I-group which stands in orthoposition to the N=N- group, '0 stands, for instance, for hydrogen, alkyl, aryl, COOH or COOR. (R.'=alkyl), y for a CH=CH- or a CI-Iz-CH2- group, and z fora N02- or NHz group,'-

nitroor amino-group. I

The combination of the aforesaid coupling com-' ponents and diazotized orthoehydroxylated or orthorcarboxylateddiazotization components to produce azo-dyestufis proceeds las is usual for pyrazolones, in an acid or an alkaline medium. As will be apparent from the foregoing formulae of the coupling components, besides the formation of the pyrazolone-azo-dyestuff a further azo-dyestufi formation may occur, for example with the residue of one of the aminophenolor amino,- hydroxynaphthalene derivatives named (see for instance Formulae 13 and 20); In this case'it is possible to prepare as maybe desired mixed dye- I stuffs in respect of the diazotization components,

since, apart from the difieren tcoupling powers of the diazo components, the coupling powers of the various residues of the coupling components are ':also different. azotized ortho-aminocarboxylic acids couple more Thus, quite generally the dieasily than the diazotized ortho-amino-hydroxy compounds and the pyrazolones more easilythan. the 1-hydroxynaphthalene-3-sulfonic acid residues. Thus, by combining l mol of diazotized l-aminobenzene-2-carboxylic acid in an acetic acidmedium with 1 mol of thecompound .oithe Formula 19, and then combining the mono-azodyestufi further in an alkaline medium with 1 mol of diazotized l-hydroxy-2-aminobenzene-4-suland. then to proceed with the conversion of the ionic acid, there is produced a dyestuif of the formula:

H S 0311 S 03H Such mixed dyestuffs, but containing metal,

may also be prepared easily by the use of diazotization components which only during metallisation pass into ortho-hydroxyor ortho-carboxyazo derivatives.

The conversion of the azo-dyestuffs into metal compounds may as arule be conducted by treatment of the finished dyestuff with a salt, hydroxide or oxide of one of the metals hereinbefore referred to, for example copper sulfate, copper chloride, copper hydroxide, ammoniacal copper oxide, copper tetramine sulfate, derivatives of copper tetramine sulfate in which the ammonia residues are replaced by the residues of organic bases, such as methylamine or pyridine, chromium chloride, chromium sulfate, chromium fluoride, chromium formate, chromium acetate, chromium hydroxide, sodium chromite, sodium glyoerine chromite, nickel chloride, nickel sulfate, cobalt chloride, manganese chloride, andso on. The

, metallization may be conducted on the fibre or advantageously in substance by treating or warming a solution or suspension of the dyestufi' in adopen vessel or under pressure. The same metal liferous dyestufis can also be obtained by metallizing dyestuffs which have been prepared from the l-aryl-5-pyrazolones here in question and from diazotization components which contain no OH- or COOH-group in ortho-position but contain in ortho-position a substituent which in the course of the metallization becomes converted into an OI-I- or COOI-I-group, such as a chlorine or bromine atom or an OC'H3-group (which substituents are converted into the OH-group during metallization) or a COO-alk'yl-group which is then saponified to a COOH-group. The metallization can also occur simultaneously with the coupling of the azo-dyestuff; this procedure is particularly to be recommended in the production of copper compounds.

The new dyestuffs, therefore, are complex metal compounds of dyestuffs such as the following: i

it being unknown in whatmanner -the metal is bound at the ortho-hydroxy or ortho-carboxyazo-group; reference must also be made to the further possibilities afforded by the diazo components hereinbefore mentioned and the formulag; of the coupling components given by way of exam le.

. The dyestuffs of the present invention are "accordingly complex metal compounds of a20- dyestuffs of the gen'eralformula and in 4-position with the azo-residue, y for a c onyersion product of a' nitro-group, The characteristic properties of the new metalaliferous dyestufis are conditioned by the group- S 11 SOaH of the dyestuffs, their high fastness to light and their aflinity for vegetable fibres, as will be evident from a comparison of the properties of the individual products described in the examples which follow.

When prepared in substance the new products f 9 t I o=N 65 coon .N CH=GH I N=N-CC H I II S 0311 s 0311 H o constitute in-"t't; dry state senate brown or blackish powders which are soluble in water to yellow to orange, brown, greenish, olive and {H blackish solutions from which they are adsorbed 7 by cellulose fibres yielding dyeings of similar CH=CH- or a CH2CHz-group and z for the which in particular is responsible for the jshade.

Ewample 1 13.7 parts of 1 aminobenzene-2-carboxylic acid are diazo'ti'zed in the usual manner and'coupled inan'acetic' acid'medium'with 45.1 parts of the 3-methyl-5-pyr azo1one of the formula 1? 8031-1 SOaH The dyestuff is isolated, dissolved in 1000 parts of water, containing an excess of sodium carbonate, and the solution is treated'with phosgene at 40-50 C". When this treatment is ended,;'that is to say when' a free amino-group is no longer present, the dyestuff isolated and dried. It is a yellow powder which dyes cotton fast yellow shades.

The dyestufi thus prepared is suspended in 3000 parts of water and the suspension is mixed with an ammoniacal copper oxide solution corresponding with 35 parts of crystallized copper sulfate. The whole is stirred at 7 0 .C of about 55 1 hour, whereupon the metalliferous dyestufi is filtered with suction and cautiously dried. :Th dry dyestuff containing copper is a brown powder which dyes vegetable fibres and'artificial silks of regenerated cellulose excellent yellow shades fast to light. The non-metallized dyestufi corresponds thus to the formula sonar S0311 u The conversion ofthe dyestuff into its copper complex may also be conducted in an acid medium by treatment with a copper salt such as copper sulfate.

By combining the diazo compound from 13.7 7

partsof l-amino-benzene-2 carboxylic acid with 45.3 parts of the 3-methyl-5-pyrazolone of the formula 1 treating the dyestuff with phosgene and converting the product into the complex copper compound as above described there is obtained a dyestufi containing copper which, when dried, constitutes a yellow-brown powder and dyes cotton fast yellow shades, resembling in shade and properties those of the stilbene product.

By suspending 59.9 parts of the dyestuff described in the first paragraph of this example in about 3000 parts of waterand treating the suspension with a solution of 30 parts of crystallized nickel sulfate in 200 parts of water for 1 hour at '7080 C. in the presence of sodium acetate there isobtained the complex nickel compound of the dyestufi which, when dried, is a brownish powder which dyes cotton fast'yellow shades with a somewhat orange hue.

The same shades are obtained by first dyeing with the non-metallized dyestufi in the manner usual for dyeing with direct dyestuffs and then lafter-coppering or after-treating the dyeing with i Example 45 parts of the 3-methyl-5-pyrazolone of the formula Bil-C i or of the formula SOaH SOaH S 0311 S 03H solved in water together with the quantity of sodium carbonate necessary for forming the sodium salt, 13.6 parts of sodium acetate are added and the solution is coupled in the usual manner with a solution of the diazo compound from 13.7 parts of 1-aminobenzene-z-carboxylic acid in the presence of 25 parts of copper acetate. When the diazo compound has disappeared the whole is made alkaline with ammonia, gently heated and filtered after the addition of common salt. The cupriferous dyestuff thus obtained shows the same behavior as the cupriferous dy'estuff described in the preceding example. The replacement of phosgene by thiophos gene leads to a similar product. So also does the replacement of the 1-aminobenzene-2-carboxylic acid by the 1-amino-4-chlorobenzene-2- carboxylic acid, by 1-amino-4-nitrobenzene-2- carboxylic acid, by l-amino4-methylbenzene-2- carboxylic acid or by l-amino-l-ethoxy-benzene- 2-carboxylic acid. i

If there is used as parent material for making the metalliferous dyestuff the 3-carboxy-5- 2 pyrazolone of the formula formula (obtainable from benzoylacetic ester), dyestuffs having similar valuable properites are obtained. The formula of a non-metallized dyestufi of this are dissolved in 500 parts of water and 11 parts group is for instance coon C N COOH II SOaH H 0 of sodium carbonate and converted into the corresponding urea by the introduction of phosgene at ater'nperature of 40-50 C. When the free amino group has disappeared the urea is isolated.

46.2 parts of the urea thus obtained are dis- Quite similar dyestuffs are obtained if the CO- group of the urea residue is replaced by a heterocyclic amidine-like nucleus. Such a product can beobta-ined, for example, by adding 90.2 parts of the B-methyI-S-pyrazolone named in .75

required, this secondaryproduct can be converted into a tertiary condensation product by replacing the remainin 'chlorinefatom in the 'cyanuric ring by treatment' with9.3 parts of aniline in known manner. If now the Sodium salt from 53.5 parts of this condensation product is combined with the diazo compound from 13.7 parts of 1-aminobenzene-'2-carboxylic acid thereis obtained a dyestufi Whose metal compounds resemble themetal compounds of the azodyestufi of Example 1: for instance, the copper compound dyes cotton yellow shades very fast to light. The formula of the non-metallized dyestuff is therefore:

If in the preparation of such dyestuffs, or of the condensation products from animo-aryl-pyrazolone and cyanuric chloride'from which they are derived the 18.4 parts of cyanuric chloride are replaced by 11.5 parts of 2:6-dichloro-4-methylpyrimidine or 19.9 parts of dichloro-quinazoline or 21.4 parts of phenylchlorotriazine, dyestuffs having very similar properties are obtained. .The formula of such a non-metallized dyestuif is:

'I] SOaH SOaH in the form of the neutral sodium salt are dissolved in water together with the necessary quantity of sodium carbonate, and after addition of 13.6 parts of crystallized sodium acetate the solution is coupled with the diazo compound from 13.7parts of 1 aminobenzene-2-carboxylic acid.

A e s me m ar of d m rbqnaie are added to-thesuspension of the mono-azo-dyg stuff. The mono-azo-dyestuff thereupon dis solves and is then further coupled with a diazo solution prepared as usual from 18.9 partsof 1- hydroxy-Z-aminobenzenel-sulfonic acid. 1 The dyestufi is--isolated by salting-out, filtered-with suction and dried. When dry it is a dark brown powder which dyes cotton and similar fibres yellow-brown shades.

The dyestufi thus obtained having the formu- 1a CHa is soluble in water to axbrown -yellow solution and dyes cotton and artificial silk from regenerated celluloseubrown yellow, shades which are very fast to light. 1 By treating the dyestuff of the above formula with agents yielding other metals than copper,

such as salts of manganese, iron, cobalt, nickel, chromium-andso on, thereare obtained the coron; 2 4 V p 1 H. I p i /N\ N=(\J N=N- -(|'|J so H so H /N H 0 H H H O a a H \C S a S03 9) I OOOH I Hooo nc" ze x .mpi a responding metal complexes which dye vegetable i 9238 parts of the '3-methyl-5-pyrazolone of-the fibres slmllar yellow-brown Shades v 'Ihemetal complexes may also be produced by formula V.

ICH3 CH: C=N N= Hts-0 n o H o- H, i

soan an after-treatment on the fibre in the manner illustrated in Example 1.-

If in the present example the l-aminobenzene- Z-carboxylic acid is replaced by a substituted anthranilic acid such as l-aminol-chlorobenzene 2-carboxylimacicl or. .1..=amin0-A +nitro enz -3ec boxylic acid and the ortho-aminophenol is replaced by one of its substitution products, such as 4-chloro-2-amino-l-hydroxybenzene or 4- or -nitro-2-amino-l-hydroxybenzene, or by one of the other ortho-hydroxyamino compounds of the benzene or naphthalene series named in the introduction, dyestufis are obtained which can likewise be converted according to the foregoing directions into complex copper or other metal compounds. In this connection the following may be said.

Whilst replacement of the 1-aminobenzene 2- carboxylic acid by the aforesaid substitution products of this body influences the shade of the final dyestuff only to a small extent, substantial displacements of the shade can be obtained by suitable selection of the ortho-hydroxy-diazo compound, whereby, for instance, products which dye orange to brown-yellow and reddish shades can be prepared. Thus for example, the copper compound of the product from 1 mol of the pyrazolone-urea derivative of the first paragraph of this example with 1 molof diazotized l-aminobenzene-Z-carboxylic acid and 1 mol of diazo tized 5-nitro-2-amino-l hydroxybenzene dyes brown-yellow shades; replacement of the 5-nitro- Z-amino-l-hydroxybenzene derivative by diazotized 1-amino-2-hydroxynaphthalene-4-sulfonic acid leads to a copper compound which dyes reddish-brown shades.

If in this example the 3-methyl-5-pyrazolone is replaced by the corresponding 5-pyrazolone-3- carboxylic acid there are obtained analogous dyestuffs which, especially in the case of the copper compounds, dye vegetable fibres shades "which are extremely fast to light. Furthermore, the derivatives of the other l-aryl-5-pyrazolones referred to in Example 2 lead to similar products.

If in the preparation of the dyestuffs from the urea pyrazolone derivatives of the present example the l-aminobenzene-2-carboxylic acid is also replaced by an ortho-aminophenol, metalliferous dyestuifs dyeing darker shades are obtained. Thus, the copper compound of the dyestuff' of the formula 01 coon dyes cotton brown-red.

Example 4 59.9 parts of the dyestui'f from diazontized 1- aminobenzene-2-carboxylic acid and the 3- methyI-S-pyrazolone of the formula s 03H s 03H G=N\ I l It is then suspended in waterand converted into a complex copper compound by treatment with an agent yielding copper, for instance in the manner indicatedin Example 1. When dry, the cupriferous dyestufi is a brown-yellow powder which dyes vegetable fibres yellow shades. The formula of the non-metallized dyestufi is:

COOH

The cupriferous dyestufi can also be produced on the fibre. If the dyestufi obtainable as described in the first paragraph of this example is treated with agents yielding metals other than copper, for example, with a salt of nickel, cobalt, manganese, chromium or iron, there are obtained the corresponding complex metal compounds which dye the fibre yellow shades or shades which vary more or less from yellow.

The same products can also be prepared by first treating the 5-pyrazolone serving as parent material with the acidylating agent and then combining the acidylated pyrazolone with the diazo compound and converting the product into the complex metal compound; alternatively, the complex metal compound of the dyestufi referred to at the commencement of this example may be treated with the acidylating agent.

7 As acidylating agents there may be used in the appropriate manner the anhydrides or acid halides of'carboxylic or sulfonic acids, for example of acetic acid, butyric acid, substituted benzoic acids such as pari-nitrobenzoic acid, cinnamic acid, benzenedicarboxylicacids such as, among others, terephthalic acid, hexahydro-benzoic acid, oxalic acid, phenylacetic acid, iurane-carboxylic acid, benzenesulfonic acids, substituted benzenesulfonic acids such as para-toluenesulfonic acid, and many others.

Further valuable similarly constituted dyestufis are obtained if the initial dyestufi of the COOH ('31 N 59.9 parts of the dyestuff from diazotized 1- aminobenzene-2-carboxylic acid and the 3- methyl-S-pyrazolone of the formula solved in about 300 parts of Water, and at -5 G.

in theform of -the neutral sodium salt are disthe solution is introduced into an aqueous suspension of 18.4 parts of cyanuric chloride. When condensation is finished there is introduced into the mixture a solution of; the sodium compound from 25 .7 parts of"4 amino 4'-hydroxy-azoben- Zene-B carbOXyIic acid in about 100- parts of water. The whole is heated at 50-55" C. and the liberated acid is neutralized by the addition of sodium bicarbonate. When condensation is finished the reaction product is salted out and filtered with suction. The dyestuff of the formula can be converted as such into a metal compound; the copper compound dyes cotton oryiscose artificial silk, for example, fast yellow shades.

The third chlorine atom of the cyanuric ring may also be exchanged. For this purpose the freshly filtered non-metallized dyestuff is dissolved in about 800 parts of water and the solution is boiled for about 1 hour with 9.3 parts of aniline for replacing the remaining chlorine atom of the cyanuric residue. The excess of aniline is then expelled by steam distillation, the solution is filtered and the dyestuff is salted-out, filtered N H M MGOH I t i pure'yellow shades of excellent fastness to light.

The analogous dyestuff in which the CH=CH- group is merely replaced by a CI-Iz-CIIz-group has similar properties. If the dyestuff of the first paragraph of this example is suspended in about 3000 parts of water and the suspension is heated with a solution of 30 par-ts of crystallized nickel sulfate in 200 parts of water in the presence of sodium acetate for, one hour at '70- 80 0., there is obtained a complex nickel compound which, when dry, is a brownish powder and dyes cotton fast yellow tints.

Like shades are obtained by first dyeing the fibre with the non-metallized dyestufi in the coon its

manner usual for direct dyestuffs and then aftercoppering the dyeing or after-treating it with a nickel salt in known manner. By treating with an iron salt a dyeing produced by means of an alkali salt of the dyestufi there are obtained dull yellow shades; by treatment with cobalt salts yellow shades, with chromium salts somewhat greenish-yellow shades and with manganese salts yellow shades are obtained. Those complex metal salts may also be prepared in substance by known methods.

By metallizing according to the data of the preceding paragraphs the similarly constituted dyestufi of the formula with suction and dried. The dyestuff so obtained dyes cotton powerful yellow shades. v

This dyestufi having presumably the formula which is obtained as chief product if phosgene is run into a solution of 60 parts of the azo-dye- 000E ,N'fl

N=N -o g g SOIH 08H 0 its 00011 (I; is suspended in about 3000 parts of Walter and the suspension is mixedwith an ammoniacal copstufi of the formula per oxide solution corresponding with 50 parts of CH8 crystallized copper sulfate. The whole is heated at (so-70 c. and stirredfor about 1 hour at this temperature. 1 The sparingly soluble complex N CH=OH NHa copper compound precipitates and after cooling and, if necessary, completely salting-out, it is fil- I II S aH SOsH tered with suction. 006R 7 H 0 When dry, the cupriferous-dyestufi isa brownish powder which dyes cotton, artificial silk from 75;; regenerated cellulose and similar fibres. stable and J26 parts of Lamina-4-hydroxya2obenzene- 3'-carboxylic acid in 400 parts of water contain- 2,221,3 11 ing 30 parts of sodium carbonate until almost 1 -ary1-5-pyrazolone of the formula no free amino-group is present, there are 010- tained dyestuffs whose tints are very similar to I the corresponding metallized dyestufis contain- 5 ing the cyanuric ring. 1 /N- CH=CHONHQ 5 The replacement of 1-aminobenzene-2-carboxylic acid by an ortho-aminophenol or an ortho- I 50311 $0311 aminonaphthol in the synthesis of such dyestufis leads to copper compounds which dye brown and one equi le proportion of cyamlric ch 0- 0 shades, This is the case, for example, with the ride is condensed in an analogous manner with dyestuffs of the general formulae 27.7 parts of 4-aJnino-azobenzene-4-sulfonic coon 5 NO on I N=N-C-C I II SOaH SOBH coon I0 and sosn son-I C=N\ I 5 SOaH N=NCC I II coon I H O OH in which :1: stands for instance, for I) acid and 9.3-parts of aniline or 10.7 parts of I A l monomethyl-aniline or para-toluidine. There is obtained a yellow dyestuff which dyes cotton fast and N shades and can be converted into a complex copper compound in the manner already described. 5 I The replacement of the 4-amino-azobenzene-4'- H H sulfonic acid by the azo-dyestufifrom diazotized o H I 2-amino-naphthalene-4:8-disulfonic acid and \l;@ I meta-toluidine followed by diazotization and coupling with a further molecule of meta-toluidine Finally, if in the first phase of this example leads to a product which when converted into the 40 the primary condensation product of the formula copper compound constitutes a browner dyestuff,

E I I I C=N p N 00011 l /NQCH=CH NH-(|J o-c1 N: so H o H H J) a I \C 0 t1 so is condensed with 2 equivalent proportions of 4- which corresponds for example to the following amino-4'-hydroxy-azobenzene-3-carboxylic acid formula of a non-metallized dyestuff:

=N\ N\ I I N=N C 0 son H N\ H OH H 7 I g S s a V a s OOH I HNGCH; SOsH and the tertiary condensation product is treated Example 7 with anagent yielding metal, there are again I obtained metallii'erous dyestuffs which dye yelf parts the 3 methyl S'pymZOIOne of the I ormula low shades.

w I Example 6 I 'N 0H=0H- NH: The primary condensation product prepared according to the first paragraph of ExampleS froml scan 03H equivalent proportion of the dyestuff from diazo- 0 tized 1-aminobenzeneJ-carboxylic acid and the are dissclvedin 500 parts'of water together with 7 SOaH O of water, 13.6 parts of sodium acetate are added and the solution is coupled with a diazo solution from 13.7 parts of l-aminobenzene-2-carboxylic acid. Then there are added an aqueous solution of 11 parts of sodium carb'onateand a diazo solution from further 13.7 parts ofl-aminobenzehe-Z- carboxylic acid. When coupling is finished, the

dyestuff is salted out, filtered with suction and dried. It is a yellow-brown powder which dyes cotton yellow-brown shades. By converting the dyestuff into a copper or nickel compound according to the directions in Example 1, dyestuffs are obtained which dye cotton yellow-brown shades of excellent fastness' to light. The nonmetallized dyestuff corresponds to the formula finished, the dyestuff is isolated as usual. B treating it with agents yielding metal according to the directions of Example 1, for example with a salt of copper or nickel, metalliferous dyestuffs are obtained which dye vegetable fibres fast 5 shades which are yellow-brown in the case of the copper compound and orange-brown in the case of the nickel compound. The non-metallized dyestufi? corresponds to the formula (EH; 3 O=N 6 Q t t i 'QoH=oH N("JItl sou: N=N- C O H l SOzH OaH I 00011 Example 8 there can be prepared a large number of further 71.6 parts of the mixed urea of the formula dyestuffs which can be converted by treatment" (IJHa ,o=N

obtainable as described in the first paragraph of Example? are dissolved in the form of the sodium the mono-azo-dyestufi is finished, there are added an aqueous solution of 11 parts of sodium carbonate and then slowly a diazol solution from 18.9 parts of 2-amino-1-hydroxybenzene-4-sulfonic acid. When coupling to a disazo dyestufiis with agents yielding metal, such as agents yield- I ing copper, according to the directions'given in Example 1, into very Valuable dyestuffs contain- 1 ing metal which dye textile fibres various shades of brown. Brown dyestuffs, for example, are.

the copper compounds of such azo-dyestufi as the various dia'zo compounds are used, there are obtained, even from otherwise the same parent materials, dyestuffs or metal compounds which indeed have similar dyeing properties but nevertheless exhibit appreciable variations.

thus obtained having the formula or of the formula Ewample 9 45.1 parts of the 3-methyl-5-pyrazolone ofthe formula om I S OaH- $02K or of the formula s om 's OaH in the condensation by means 01' sodium carbonate. For exchanging the remaining chlorine atom of the cyanuric ring the secondary. condens tion prodl i l is treated in known manner are dissolved in 200 parts of water with addition of sodium carbonate in the quantityrequired for forming the neutral sodium salt and the solution is then mixed withthe diazosolution from 13.? parts of 1-aminc-benzene-Z-carboxylic acid with the addition of a solution of parts of copper sulfate in dilute ammonia. There is thus formed.

the copper compound .of the disazo-dyestufi" which, when isolated in known manner, dyes cotton fast brown shades. If in the preparation of the intermediate product for this dyestuif according to the first paragraph of this example the 23.9 parts of 2-amino-5 hydroxynaphthalene-l-sulfonic acid are replaced by a like quantity of 2-amino-8-hydroxynaphthalene-6-sulfonic acid there is obtained a dyestuff containing copper and dyeing similar shades, whilst replacement of the 2-amino-5-hydroxynaphthalene-'7- sulfonic acid by. 31.9 parts of 1-amino-8-hydroxynaphthalene-3:G-disulfonic acid leads to a product containing copper which dyes appreciably deeper and redder shades. The formula of the non-metallized dyestufi corresponding to th last named product is the following:\.

COOH

Deep brown is for example the copper compound After the excess of primary,

of the azo-dyestufi: of: the, formula Complex metal compounds which dye yellow shades can be obtained by replacing in the preparation of the intermediate product the 2-aminc--hydroxynaphthalene-'7-sulfonic acid by l-amino-3-hydroxynaphthalene, 1 (4 aminophenyl) -3-methy1 5 pyrazolone, I 1- (B'eaminophenyl) -3-carboxy 5 pyrazolone, para-aminoaceto-acetic anilide and so on. The formula of such a non-metallized dyestuff is for example:

i 80:11 SOBH H OOH Example 42.9 parts of the ternary condensation product of the first paragraph of Example!) are dissolved to a, neutral solution which is mixed with a 'diazosolution from 6.9 parts of l-aminobenzene-2-carboxylic acid to which sodium acetate has been added. The whole is stirred until the diazo compound has disappeared and isthen rendered alkaline and mixed with diazo compound from 9.4 parts of 1-hydroXy-2-aminobenzenel-sulfonic acid. After this diazo compoundlhas also disappeared, the whole is filtered and the filtered dyestuff is suspended in 1000 parts of water. parts of copper acetate are added and the suspension is heated for some time at 80 CL, after which the copper compound is separated by filtering. Theproduct dyes cotton yellow-brown shades.

SOaH

A yellowish-brown dyestuff is likewise obtained by combining 42.9 parts of the condensation product of the first paragraph of this example with the diazo compound from 22.3 parts of z-amino--chloro 1 hydroxybenzene-G-sulionic acid and converting the dyestufi thus obtained into its copper compound.

Further brown dyestufis are obtained by combining 1 mol of the aforesaid ternary condensa- II II N\ /N H 0 0 I N NH tion product in difierent orders of succession with 1 mol of a diazotized l-aminobenzene-Z- carboxylic acid; 1 mol of an 'ortho-hydroxy-diazo corfipound for example, l-hydroxy-Z-amino- 4-nitrobenzene or with 1 mol of a diazotized amino-azo-dyestufi, for example with the diazotized azo-dyestuff from 1 mol of diazotized. 1-.

and 2 stands for the radical .of an azo'dyestufi What I claim is: 1. The .metal compounds of the azo-dyestuffs corresponding in the free state to the general formula Q-Q s03]: s 03H 1 Y in which R stands for a nucleus of the group consisting of aromatic nuclei of the benzene and naphthalene series, a: standsfor a lake-forming group in ortho position to the --NV=N-group, ry stands for the radical of a S-pyrazolone which is combined in l-position with the radical by a connecting link of the general formula 12 standing for a member of the group consisting of 0:0 and the radical .of a heterocyclic six membered ring system whose heterocyclic sixmembered ring consists of carbon and nitrogen atoms of which at least 3 and at the most 4 are carbon atoms and at least 2 and at the most 3 are nitrogen atoms, the

groups being linked to the carbon atom of the groupings of the heterocyclic rin Which products form yellow to brown powders, dissolve in water to yellow to orange, brown and olive solutions, and dye cotton fast'yellow to orange, brown and olive tints which are particularly fast to light.

2. The metal compounds of the azo dyestuffs corresponding in the free stateto the general formula y s 0311 s 0311 in which R stands for a nucleus of the group consisting of "aromatic nuclei of 'the benzene and naphthalene series, 1L stands for a lake-forming group in ortho position to the -N=N-group, Py stands for the radical of a 5-p'yrazolone which is combined in l-position with the iazo 'group and in 1-position with the radical scan i onr R1eN=-NR2 wherein the symbols Rland R2 represent aromatic nuclei selected from the group consisting of the benzene and naphthalene series, one of the two aromatic nuclei being linked to the radical" SOaH sour p by a connecting link of the general formula -Nv--N- 1'1 t 11 standing for a member of the group consisting of 0 II t i 0 and the radical of a heterocyclic six-membered ring system, whose hetero-cyclic six-membered ring consists of carbon and nitrogen of which at least 3 and at the most 4 are carbon atoms and at least 2 and at the most 3 are nitrogen atoms,

the

groups being linked to the carbon atom of the groupings of the heterocyclic ring, which products form yellow to brown powders, dissolve in water to yellow to orange, brown and olive solutions and dye cotton fast yellow to orange, brown and olive tints which are particularly fast to light.

3. The copper compounds of the azo-dyestuffs corresponding inthe free" state to the general formula i soar: son:

in which R stands for a nucleus of the group consisting of aromatic nuclei of the benzene and naphthalene series, :1: stands for lake-forming group in ortho position to the -N=N-group, Py stands for the radical of a 5-pyrazolonewhich is combined in l-position with the radical and in 4-position with the azo-group, y stands for a connecting link of the group consisting of CH=CH and -CH2CI-Iz, and 2 stands for the radicalof an azo-dyestuff of the general formula R1N=N--R2 wherein the symbols R1 and R2 represent aromatic nuclei selected from the group consisting of aromatic nuclei of the benzene and naphthalene series, one of the nuclei R1 and Rc'being linked to the radical 0&3 scan som by a connectinglink of the general formula N-r N 11 standing for a member of the group consist- R1 and R2 ing of :0 and the radical of a heterocyclic sixmembered ring system whose heterocyclic sixmembered ring consists 'of carbon and nitrogen atoms of which at least 3 and at the most 4 are carbon atomsand at least 2rand are nitrogen atoms, the

in which R-stands for a nucleus "of the group consisting of aromatic nuclei of the benzene and naphthalene series, .7: stands for lake-forming group in ortho position to the N=N-group,

Py stands for the radical of a -.pyrazolone which is combined in 4-position with the azo group and in l-position with the radical and 2 stands for the radical of an azo dyestufi of the general formula R1-N=N-R2, wherein the symbols R1 and R2 represent aromatic nuclei selected from the group consisting of aromatic nuclei of the benzene and naphthalene series, one ofthe nuclei R1 and R2 being linked to the by a connecting link of the general formula 11 standing for a member of the group consisting of 0:0 and the radical of a heterocyclic six-membered ring system whose heterocyclic sixmembered ring consists of carbon andnitrogen atoms of which at least 3 and at the most 4are carbon atoms and at least 2 and at the most 3 are nitrogen atoms, the I groups being linked to the carbon atom of the groupings of the heterocyclic ring, which products form yellow to brown powders, dissolve in water to yellow to orange, brown and olive solutions, and dye cotton fast yellow to orange,

brown and olive tints which are particularly fast to light.

at the most 3 atom of the the azo dyestuffs 5. The copper compounds of the azo-dyestuffs corresponding in the free state to the general formula SOsH SOaH in which R stands for a nucleus of the group consisting of aromatic nuclei of the benzene and naphthalene'series, :1; stands for a lake-forming group in ortho-position to the N=N-group, Py stands for the radical of a 5-pyrazolone which is combined in l-position with the radical and in 4-position with the azo-group, :1; stands for a connecting link of the group consisting of '-CH=CH-- and --CH2CH2-, and 2 stands for the radical of an azo-dyestufi of the general formula R1N=N-R2, wherein the symbols R1 and R2 represent aromatic nuclei selected from the group consisting of aromatic nuclei of the benzene and naphthalene series, one of the nuclei R1 and Rzbeing linked to the radical S 0 3H 0 3H by a connecting link of the formula which products form yellow to brown powders, dissolve in water to yellow to orange, brown and olive solutions, and'dye cotton fast yellow to orange, brown and olive tints which are particularly fast to light.

6. The copper compounds of the azo dyestuffs corresponding in the'free state to the general formula SOaH S0311 in which R stands for a nucleus of the group consisting of aromatic nuclei of the benzene and naphthalene series, 0: stands for a lake-forming group in ortho-position to the N=N group, Py stands for the radical of a 5-pyrazolone which is combined in l-position with the radical Game-OZ and in 4-position with the azo group, and 2.

stands for the radical of an azo dyestuff of the general formula R1N=N R2 wherein the sym bols R1 and R2 represent aromatic nuclei selected from the group consisting of the benzene and naphthalene series one of the nuclei R1 and R2 being linked to the radical by a connecting link of the formula N C.. N I I II I v H o H which products form yellow to brown powders, dissolve in waterrto yellow to orange, brown and olivesolutions, and dyecotton fast yellow to orange brown, and olive tints which;- are particularlyfast to light.

7.;The metal compounds oitheazqdyestuffs having in the free state the formula in which Ri stands for a nucleus of the group consisting of nuclei of" thesbenzeneand naphthalene series, or stands for a lake-forming group in ortho-position to the N=,N- group, Py

I S O=H tom in; which R1 and R2 stand for nuclei of thebenzene series, :2; stands for a lake-forming group in ortho-position to the -'N=N group, 1 stands for a connecting link of the group consisting of for the radical of a S-pyrazolone which is linked in l-position to the radical l SOQH soul and in 4-positi0n to the azo group, which products form yellow to brown powders, dissolve in water to yellow;to orange and brown solutions and dye cotton similar tints fast to light. 8. The copper compounds of the azo-dyestufis having in the freestate' the formula and in ll-position to the azo-g'roup, which products form yellow to brown powders, dissolve in water'to yellow to orange and brown solutions and dye cotton similar tints fast to light.

9. The copper compounds of the azo dyestuffs corresponding in the free state to the general formula in which R1 and-Rzstand for nuclei of the henzene series, a: stands for a lake-forming group in orth'o position to the N=N'- group and Py standsfor the radical of'a 5-pyrazolone which is linked in l-position to the radical and in 4-position to the azo group, which prod ucts form yellow to brown powders, dissolve in water toTyellow .tb orange. .and brown solutions and dye cotton similar tints iast*to"light; 10. ,The metal compounds oftheazmdyestufis having in the free state the'general formula s: lit 0 1'1 stands forthe radical of a 5-pyrazolone which is 2 combined in l-position'with the radical SOaH k S0311 SQsH V and in ii-position with the azo-group, y stands for a connecting link of the group consisting of CH-5 CH and CI -I2 CH2--, and R2 and Ra, stand for nuclei selected from the group consisting of aromatic nuclei of the benzene and naphthalene series, which products form yellow to-brownpowders, dissolve in water to yellow to orange, brown and olive solutions, and dye cotton fast yellow to orange, brown and olive tints which are particularly fast to light.

l lq'The copper compounds of the azo-dyestuf fs having in the free state the general formula s oan S0311 in which R1 stands for a nucleus of the group, consisting of nuclei of the benzene and naphthalene series, :1: stands for alake-forming group in ortho-position to the -N=N group, Py stands for the radicalof a v 5-pyrazolone which is combined in l-position with th radical SOsH SIO3H c and in 4-position to the azo-group, 1; stands for a connecting link of the group consisting of CH=CH and CHz-=CHz, and; R2 and R3 H O H I SOaH SOaH stand -for nuclei selected from the group consist ing of aromatic nuclei of the benzene and naphthalene series, whichproducts form yellow tobr'own powders, dissolve in water to yellow to orange, brown and olive solutions, and dyecotton fast yellow to orange, brown and olive tintswhich are particularlyvfast to light.

"112;:The'copper compounds of the azo-dyestufis having in the freestate the general formula in which R1 stands for a nucleus of the benzene series, a: standsfor a lake-forming group in ortho-posltion to the -N N-group, Py stands for the radical of a 5-pyrazolonewhichlscom bined in l-position with the radical r SOaH SOaH and in 4-position with the azo-group, 1/ stands to brown products, dissolve in water to' yellow to orange, brown and olive solutions, and dye cotton fast yellow to orange, brownand olive tints, which are particularly fast tolight. -l

13. The copper compound of the azo dyestuff having in the free state the formula which yields'on the vegetable fiber yellow brown tints fast to light.

14. The copper compound of the azo-dyestuff having in the free state the formula which'yields on the vegetable fiber yellow'tints fast to light.

.15. The copper compounds of the azo-dyestufis corresponding in the free state to the general formula V in which Py stands for the radical of a 5-pyrazolone which is combined in l-position with the radical and' in i-posiltion with .the' azo-group; and y stands-for a: connecting 'linkof the group consisting of CH==CH-- and-CI-lz-CH2-, which products yield yellow tints on the vegetable fiber which are fast to light. I a, a

16. The copper compound of the azo-dyestuff corresponding inthe' free state to the formula which yields on the gveget'able fiber yellow tints fast to light. I V e V 17. The copper compounds of the azo dyestuffs having in the free state the general formula in R1 stands forja nucleus of the group consisting of nuclei of the benzene and naphtha- "lenev series, a: stands for a lake-forming group in ortho position to the N=N group, Py stands 'fo'r the radical of a 5-pyrazolone' which is combined in 1-position with the radical and ind-position 'withthe jaz o group and R2 and i R3 stand for nuclei selected from the group consisting of; the benzene, and naphthalene series. Which productsuform yellow to brown powders, dissolve in water to yellow to orange, brown and v coon ukvetuuucshg and dye; cotton yellow; to

orange, lbrownandlolive tints fwhichare particu 70 

